Catalyst‐Free Dynamic Covalent C=C/C=N Metathesis Reaction for Associative Covalent Adaptable Networks

Author:

Li Pengyun1,Jiang Xin1,Gu Ruirui1ORCID,Tian He1ORCID,Qu Da‐Hui1ORCID

Affiliation:

1. Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering East China University of Science and Technology 130 Meilong Road Shanghai 200237 P. R. China

Abstract

AbstractCovalent adaptable networks (CANs), leveraging the dynamic exchange of covalent bonds, emerge as a promising material to address the challenge of irreversible cross‐linking in thermosetting polymers. In this work, we explore the introduction of a catalyst‐free and associative C=C/C=N metathesis reaction into thermosetting polyurethanes, creating CANs with superior stability, solvent resistance, and thermal/mechanical properties. By incorporating this dynamic exchange reaction, stress‐relaxation is significantly accelerated compared to imine‐bond‐only networks, with the rate adjustable by modifying substituents in the ortho position of the dynamic double bonds. The obtained plasticity enables recycle without altering the chemical structure or mechanical properties, and is also found to be vital for achieving shape memory functions with complex spatial structures. This metathesis reaction as a new dynamic crosslinker of polymer networks has the potential to accelerate the ongoing exploration of malleable and functional thermoset polymers.

Funder

National Natural Science Foundation of China

Publisher

Wiley

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